CN103137969B - Cathode material for secondary battery and its manufacture method - Google Patents
Cathode material for secondary battery and its manufacture method Download PDFInfo
- Publication number
- CN103137969B CN103137969B CN201210202773.9A CN201210202773A CN103137969B CN 103137969 B CN103137969 B CN 103137969B CN 201210202773 A CN201210202773 A CN 201210202773A CN 103137969 B CN103137969 B CN 103137969B
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- CN
- China
- Prior art keywords
- lithium
- sodium
- cathode material
- manganese
- precursor
- Prior art date
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- 239000010406 cathode material Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 229910004618 Na2MnPO4F Inorganic materials 0.000 claims abstract description 31
- 229910000668 LiMnPO4 Inorganic materials 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 12
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims abstract description 5
- ZRPYRHACYVTJHG-UHFFFAOYSA-L sodium fluoro-dioxido-oxo-lambda5-phosphane manganese(2+) Chemical compound P(=O)([O-])([O-])F.[Mn+2].[Na+] ZRPYRHACYVTJHG-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 26
- 239000011734 sodium Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000011572 manganese Substances 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004020 conductor Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 6
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 5
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- 239000003273 ketjen black Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000006245 Carbon black Super-P Substances 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- BBLSYMNDKUHQAG-UHFFFAOYSA-L dilithium;sulfite Chemical compound [Li+].[Li+].[O-]S([O-])=O BBLSYMNDKUHQAG-UHFFFAOYSA-L 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims 1
- 235000019289 ammonium phosphates Nutrition 0.000 claims 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims 1
- IEBUJWPMONWWDM-UHFFFAOYSA-N manganese;oxalic acid Chemical compound [Mn].OC(=O)C(O)=O IEBUJWPMONWWDM-UHFFFAOYSA-N 0.000 claims 1
- 239000011368 organic material Substances 0.000 claims 1
- 150000003016 phosphoric acids Chemical class 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 27
- 239000000463 material Substances 0.000 description 25
- 239000002904 solvent Substances 0.000 description 11
- 229910019142 PO4 Inorganic materials 0.000 description 10
- 239000011149 active material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000009831 deintercalation Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- -1 nickel metal hydride Chemical class 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical class [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- WAFGIFIAAXVSSI-UHFFFAOYSA-L fluoro-dioxido-oxo-lambda5-phosphane manganese(2+) Chemical compound [Mn++].[O-]P([O-])(F)=O WAFGIFIAAXVSSI-UHFFFAOYSA-L 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical class COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- 239000010450 olivine Substances 0.000 description 3
- 229910052609 olivine Inorganic materials 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910021570 Manganese(II) fluoride Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 229910052566 spinel group Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000013519 translation Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910010951 LiH2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910015820 MPO4F Inorganic materials 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 239000012697 Mn precursor Substances 0.000 description 1
- 229910004591 Na2FePO4F Inorganic materials 0.000 description 1
- 229910004617 Na2MPO4F Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BDKZHNJTLHOSDW-UHFFFAOYSA-N [Na].CC(O)=O Chemical compound [Na].CC(O)=O BDKZHNJTLHOSDW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005520 electrodynamics Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000002362 energy-dispersive X-ray chemical map Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The present invention discloses a kind of cathode material for secondary battery and its manufacture method.The cathode material includes lithium manganese phosphate LiMnPO4/ manganese fluorophosphate sodium Na2MnPO4F compounds, wherein LiMnPO4And Na2MnPO4F has different crystal structures.In addition, the manufacture method of cathode material can be completed by Hydrothermal Synthesiss in one step, it substantially reduces manufacturing time and cost.In addition, in the disclosure, can improve the electric conductivity of cathode material by carbon coating, so as to provide the cathode material with excellent electro-chemical activity.
Description
Technical field
The present invention relates to a kind of cathode material for secondary battery and its manufacture method.More particularly it relates to a kind of
Cathode material for secondary battery and its manufacture method, wherein lithium manganese phosphate LiMnPO4/ manganese fluorophosphate sodium Na2MnPO4F compounds can
As electrode material.
Background technology
With the use increase of portable compact electronic equipment, novel secondary battery such as nickel metal hydride or lithium is secondary
The exploitation of battery has rapid progress.Specifically, lithium secondary battery uses carbon（For example, graphite）As active material of positive electrode,
And lithium-containing oxides is used as active material of cathode, while being used as electrolyte using nonaqueous solvents.Lithium is a kind of with very high
The metal of ionization tendency, it is thus possible to reach high voltage.Therefore, lithium is used in the exploitation of the high battery of energy density.
Lithium transition-metal oxide containing lithium is mainly used as active material of cathode, and 90% or more is used for negative electrode
The lithium transition-metal oxide of active material includes layered lithium transition metal oxide（Such as, cobalt class, nickel class and cobalt/nickel/manganese
Three metaclass）.However, when layered lithium transition metal oxide is mainly used as active material of cathode, Lattice Oxygen may deintercalation
（deintercalate）And in nonideality（Overcharge and high temperature）Under be caught participate in reaction.Adversely, it may so cause
Significant problem, such as batteries caught fire.
In order to overcome these shortcomings, the active material of cathode with spinelle or olivine structural is deployed to study.
The means that problem such as stability declines because cathode degrading are solved as with lithium secondary battery, it has been shown that moved with three-dimensional lithium
The spinels lithium manganese oxide in dynamic path and the polyanion class lithium metal phosphates including olivine structural can replace stratiform
Lithium transition-metal oxide is used as cathode material.Unfortunately, because spinels lithium manganese oxide is in charge/discharge cycle mistake
Lithium is caused to be lost in journey（elution）, so cause structural instability because of Jahn-Teller distortion effects, so using it
Way is limited.
On olivine class lithium metal phosphates, iron（Fe）Class phosphate and manganese（Mn）Class phosphate has relatively low conduction
Property, it makes them be limited significantly as the purposes of cathode material.But it is coated with by nano-scale particle and carbon, the problem is changed
It is kind, it is possible thereby to use them as cathode material.
Recently it is reported that fluorophosphate（It is fluorine-containing）It can be used as polyanion class material.The chemical formula of fluorophosphate includes
Fluorine, such as, and A2MPO4F, wherein A represent Li or Na, and M represents transition metal such as Mn, Fe, Co, Ni, V or its mixture.
In theory, it is contemplated that fluorophosphate shows about high twice capacity of conventional lithium metal phosphate, because it has two Na originals
Son.Moreover, by Na2MPO4F（M=Mn, Fe, Co, Ni, V or its mixture）Situation as cathode for lithium secondary battery material
In, sodium deintercalation in initial charge step, lithium is embedded in initial discharge step, then in subsequent circulation, and the insertion of lithium/
Deintercalation is carried out in charge/discharge process.Moreover, in the situation for being used as sodium rechargeable battery cathode material, sodium it is embedding
Enter/deintercalation carries out in charge/discharge process.Disadvantageously, iron（Fe）Class LiFePO4And Na2FePO4F has relatively low fill
Electricity/discharge potential（About 3.5V）.Further drawback is these cathode materials typically by the complexity mixed via ball milling
Process causes their cost to increase come what is synthesized.
Therefore, there is demand to the inexpensive cathode material with excellent charge/discharge property in the art.
The content of the invention
The new cathode for lithium secondary battery material of present invention offer and its manufacture method, wherein lithium manganese phosphate
（LiMnPO4）With manganese fluorophosphate sodium（Na2MnPO4F）Compound can be used as cathode material.Advantageously, the compound can step conjunction
Into, and allow insertion/deintercalation of progress lithium/sodium.
In an illustrative embodiments, the present invention provides cathode material for secondary battery, wherein material LiMnPO4With
Na2MnPO4F is uniformly mixed by hydrothermal synthesis method.
In another illustrative embodiments, the present invention provides the manufacture method of cathode material for secondary battery, wherein
LiMnPO is prepared by only one synthesis step4/Na2MnPO4F compounds, and by adjusting the ratio of Li and Na in electrolyte
Example adjusts mixing ratio.
The other side and illustrative embodiments of the present invention is discussed below.
As described above, advantages of the present invention is as follows
（i）According to the present invention, the compound of various active materials is synthesized by only one synthesis step, thus is avoided that
The complicated procedures of forming mixed by ball milling used by conventional art material.
（ii）The cathode material of the present invention is shown and the level phase by the way that blended complex prepared by process is simply mixed
Same battery behavior.
Brief description of the drawings
Describe the present invention's in detail referring now to some illustrative embodiments illustrated in the accompanying drawing of the present invention
Above and other feature, these embodiments described below are merely exemplified, therefore are not limitations of the present invention,
Wherein：
Fig. 1 is shown for the exemplary final composite cathode material for lithium secondary battery that is prepared according to embodiment 1
The figure of X-ray diffraction analysis；
Fig. 2 shows the electron microscope picture of the exemplary composite cathode material prepared according to embodiment 1；
Fig. 3 shows the EDX mappings of the exemplary composite cathode material prepared according to embodiment 1（mapping）Figure；
Fig. 4 A and 4B show to include the charging at room temperature of the battery of the Exemplary cathode materials prepared according to embodiment 1/
Discharge curve；And
Fig. 5 A and 5B show to include the charging at room temperature of the battery of the Exemplary cathode materials prepared according to comparative example 5/
Discharge curve.
It should be appreciated that appended accompanying drawing is not necessarily in proportion, it presents each of explanation its general principles
Plant the expression simplified to a certain extent of preferred feature.The specific design feature of present invention disclosed herein, including, for example, tool
Body size, direction, location and shape will partly depend on specific given application and use environment.
Embodiment
Below by each embodiment of the reference present invention in detail, embodiment is shown in appended accompanying drawing, and under
Text is been described by.Although will combine illustrative embodiments describes the present invention, it is to be understood that, this specification has no intention to send out this
It is bright to be confined to these illustrative embodiments.On the contrary, the present invention not only to cover these illustrative embodiments, also to cover by
Various alternative forms, modification, equivalents and other realities in the spirit and scope of the present invention that appended claims are limited
Apply mode.
Unless stated otherwise or from context it is clear that otherwise term " about " used herein is interpreted as in this area
Normal permissible range in, such as in 2 standard deviations of average." " about " can be understood as the numerical value 10%, 9%,
8%th, in 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05% or 0.01%.Unless in addition from context clear from this
All numerical value that text is provided all are modified by term " about ".
By provided herein is scope be interpreted as the simple expression of all values within this range.For example, by 1 to 50 scope
Be interpreted as including selected from 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,
25th, 26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49 or
50 any numeral, numeral combination or all intervenient fractional values between subrange, and above-mentioned integer, for example,
1.1st, 1.2,1.3,1.4,1.5,1.6,1.7,1.8 and 1.9.For subrange, any end points by the scope is clearly considered
" the nested subrange " of extension.For example, the nested subrange of 1 to 50 exemplary range may include the 1 to 10 of a direction, 1
To 50 to 40,50 to 30,50 to 20, the 50 to 10 of 20,1 to 30 and 1 to 40, or other direction.
It should be understood that terms used herein " vehicle " or " vehicle " or other similar terms include common motor vehicle,
E.g., including Multifunctional bicycle（SUV）, bus, truck, the car of various commercial vehicles, including various ships and ship
Water carrier, aircraft etc., and including hybrid electric vehicle, electric motor car, plug-in hybrid electric vehicles, hydrogen-powered vehicle and its
Its substitute fuel car（For example, the fuel of the resource beyond oil）.As mentioned in this article, hybrid electric vehicle is that have
The vehicle of two or more power sources, for example, with petrol power and electrodynamic vehicle.
According to an illustrative embodiments, the present invention provides cathode material for secondary battery, and it is included containing manganese phosphate
Lithium（LiMnPO4）With manganese fluorophosphate sodium（Na2MnPO4F）The compound of two kinds of compounds.The mixing ratio of compound herein is x
LiMnPO4/1-xNa2MnPO4F, wherein 0<x<1.
According to an illustrative embodiment of the invention, including LiMnPO4And Na2MnPO4Both F compound is as inorganic
（LiMnPO4/Na2MnPO4F）/ organic（Carbon）Compound is provided, and wherein carbonaceous conductive material is uniformly distributed.
According to an illustrative embodiment of the invention, lithium manganese phosphate（LiMnPO4）With manganese fluorophosphate sodium（Na2MnPO4F）Tool
There are different crystal structures, wherein LiMnPO4Crystal structure there is space group Pnma, and Na2MnPO4F crystal structure has
Space group P21/n。
In this manual, the term " space group " for crystal refers to the mathematics arrangement of the symmetry elements of crystal（That is, will
Space is divided into the three dimensional symmetry group in repeatable region）.Three dimensions group is by 32 crystallographic point groups and 14 Bradley phenanthrene
（Bravais）Lattice is combined, and it can belong to one of 7 kinds of crystallographic systems.So causing space group to turn into includes the crystalline substance of lattice centering
The translational symmetry of born of the same parents and reflection, rotation and non-real rotation（improper rotation）Some groups of point group symmetry operation
Close.Moreover, different from point group, space group also contains the symmetry operation caused by translating key element, such as grasped including rotation and translation
The helical axis symmetry operation of work, and including reflecting the slide surface symmetry operation with translation.All these symmetry operations
Combination produces 230 kinds of unique space groups of total of all possible Crystals in Symmetry of description.
Hermann-Mauguin（Aka is international）Symbolic notation is one of most-often used symbolic notation in crystallography,
And it is made up of one group of up to 4 kinds symbol.The luxuriant and rich with fragrance lattice centering of the first denotational description Bradley.Three kinds of denotational descriptions are in direction afterwards
A period of time visible most significant symmetry operation in the high degree of symmetry direction of crystal.These symbols and the symbol phase used in point group
Together, but many slide surface as described above and helical axis.
In an exemplary embodiment of the present invention embodiment, space group Pnma is included in orthorhombic space group the 62nd, and
Na2MnPO4F space group P21/nIt is included in monoclinic system space group the 14th.
According to another embodiment of the present invention, the present invention provides the method for manufacture cathode material for secondary battery, the party
Method comprises the following steps：
（i）By hydrothermal synthesis method by lithium（Li）Oxide or its precursor, sodium（Na）Oxide or its precursor, manganese（Mn）Oxygen
Compound or its precursor, phosphate（P）Or its precursor or fluoride（F）Or its precursor is mixed；
（ii）The mixture obtained by hydrothermal synthesis method is heat-treated；With
（iii）Carbon material is added to the cathode material of synthesis, and passes through ball milling ground mixing material；
According to an illustrative embodiment of the invention, lithium manganese phosphate（LiMnPO4）With manganese fluorophosphate sodium（Na2MnPO4F）Tool
There are different crystal structures, and LiMnPO4With space group Pnma, and Na2MnPO4F has space group P21/n。
According to an illustrative embodiment of the invention, in step（ii）In, in argon（Ar）At 500 DEG C to passing through water under atmosphere
The mixture that thermal synthesis method is obtained is fired 6 hours.
According to an illustrative embodiment of the invention, in step（iii）In, will be from step（i）In obtained mixture with
Carbonaceous conductive material is mixed, and ball milling is then carried out, so as to provide the compound of the cathode material including being coated with carbon.
According to an illustrative embodiment of the invention, in step（i）In, the precursor of oxidate for lithium can be, but not specific
Ground is limited to, selected from lithium phosphate, lithium carbonate, lithium hydroxide, lithium acetate, lithium sulfate, lithium sulfite, lithium fluoride, lithium chloride, bromination
Any Li precursors of lithium, lithium iodide and its any mixture.
According to an illustrative embodiment of the invention, the precursor of na oxide can be, but not be certainly limited to, selected from phosphorus
Sour sodium, sodium carbonate, NaOH, sodium acetate, sodium sulphate, sodium sulfite, sodium fluoride, sodium chloride, sodium bromide and its any mixing
Any Na precursors of thing.
According to an illustrative embodiment of the invention, the precursor of Mn oxide can be, but not be certainly limited to, selected from manganese
Metal, manganese oxide, manganese oxalate, manganese acetate, any Mn precursors of manganese nitrate and its any mixture.
According to an illustrative embodiment of the invention, phosphatic precursor can be, but not be certainly limited to, selected from phosphoric acid
Ammonium, sodium phosphate, lithium phosphate, any phosphate precursor of potassium phosphate and its any mixture.
According to an illustrative embodiment of the invention, step（ii）The middle carbonaceous conductive material that uses can be, but not specific
Ground is limited to, selected from the such as super-P of the carbon material as electrode conductive material, acetylene black, Ketjen black（Ketchen Black）,
And its any carbonaceous conductive material of any combination.
Hereinafter, the present invention is more fully described with reference to the accompanying drawings.
The present invention provides cathode material for secondary battery, and it is included as the compound shown in following formula 1 as compound：
[formula 1]
xLiMnPO4/1-x Na2MnPO4F
Wherein, 0<x<1.
Hereinafter, by method of the description according to the manufacture cathode material for secondary battery of exemplary embodiment of the invention.It is logical
Cross following examples and specific manufacture method will be more readily understood.
First, the composite cathode material of the present invention can be prepared by Hydrothermal Synthesiss.For example, with distillation water as solvent come molten
Solution corresponds to the various parent materials of each expectation key element.The resulting solution for being dissolved with various materials is added into diethylene glycol（De-
Ethyl-Glycol, DEG/C4H10O3）, it is then introduced into hydrothermal synthesis device, and reacted.During the course of the reaction,
The inside of hydrothermal synthesis device is maintained at predetermined pressure.After reaction, the powder of synthesis is washed and dried, so as to only collect
Pure synthetic product.Then, synthetic product is fired in heat treatment step, to obtain LiMnPO4/Na2MnPO4F's is compound
Thing.Above-mentioned gained compound is further mixed with carbonaceous conductive material, to improve electric conductivity.As a result, active material/carbon is made to be combined
Thing.
In the composites of the present invention, various materials can be suitably mixed according to the ratio of equation 1 above, and the present invention is not
It is limited to specific mixing ratio.
The precursor of oxidate for lithium may be selected from lithium phosphate, lithium carbonate, lithium hydroxide, lithium acetate, lithium sulfate, lithium sulfite, fluorine
Change lithium, lithium chloride, lithium bromide, lithium iodide and its any mixture.
The precursor of na oxide can be, but not be certainly limited to, selected from sodium phosphate, sodium carbonate, NaOH, acetic acid
Sodium, sodium sulphate, sodium sulfite, sodium fluoride, sodium chloride, sodium bromide and its any mixture it is any.
The precursor of Mn oxide can be, but not be certainly limited to, selected from manganese Metal, manganese oxide, manganese oxalate, manganese acetate,
Manganese nitrate and its any mixture it is any.
Phosphatic precursor can be, but not be certainly limited to, and mix selected from sodium phosphate, lithium phosphate, potassium phosphate and its arbitrarily
Compound it is any.
The precursor of fluorine can be, but not be certainly limited to, selected from metal fluoride, fluoride and its any mixture
It is any.
Carbonaceous conductive material can be, but not be certainly limited to, super-P, acetylene black, Ketjen black, carbon material or its is any
Combination.
The cathode material of the obtained present invention can be used for manufacture lithium secondary battery as described above.Hereinafter, secondary electricity will be sketched
The construction and manufacture method in pond.
First, during the illustrative embodiments of the cathode material of present invention manufacture minus plate is used, according to need
By cathode material and a kind of, two kinds or a variety of conventional use of additives such as conductive material, adhesive, filler, scattered
Agent, ion conductive material and hypertensor are combined, and with appropriate solvent（Organic solvent）Slurry or thickener is made in mixture.
Then, then dried to electrode supporting substrate as the slurry by obtained by such as doctor blade method or paste.Afterwards, compacting is passed through
（For example, passing through rolling roller）, final minus plate is made.
The example of conductive material includes graphite, carbon black, acetylene black, Ketjen black, carbon fiber, metal dust etc..It can be used
PVdF, polyethylene etc. are used as adhesive.Electrode supporting substrate（Current-collector）It may include copper, nickel, stainless steel, aluminium or carbon fiber
Paper tinsel or sheet material.
By using as above made minus plate, lithium secondary battery is made.Coin, knob can be made in the lithium secondary battery
Buckle-like, sheet, cylinder, square etc..Moreover, for the lithium secondary battery anode, electrolyte and dividing plate can with for
Those in traditional lithium secondary battery are identical.
For active material of positive electrode, can use it is a kind of, two kinds, or more plant and include the transition metal combined oxidation of lithium
Thing.It is, for example, possible to use silicon, tin etc. are used as active material of positive electrode.
For electrolyte, can use the nonaqueous electrolyte of the lithium salts including being dissolved in organic solvent, inorganic solid electrolyte,
Or the compound of inorganic solid electrolyte.A kind of, two kinds or a variety of esters can be used（Such as ethylene carbonate, polypropylene carbonate
Ester, dimethyl carbonate, diethyl carbonate or methyl ethyl carbonate）, lactone such as butyrolactone, ether such as 1,2- dimethoxy-ethanes,
Ethyoxyl Ethyl Methyl Ether, or nitrile such as acetonitrile are used as nonaqueous electrolyte solvent.The example of the lithium salts of nonaqueous electrolyte can be wrapped
Include LiAsF6、LiBF4、LiPF6Etc..
In addition it is possible to use by polyolefin such as PP and/or the PE perforated membrane prepared or the porous material of such as adhesive-bonded fabric
Material is used as dividing plate.
Hereinafter, the present invention will be described in detail with reference to embodiment, but the scope of the present invention is not limited to these implementations
Example.
Embodiment
As steps described below LiMnPO is synthesized by Hydrothermal Synthesiss4/Na2MnPO4F（Ratio is 1:1）Compound.With
Scheduled volume uses LiH2PO4（99%）、NaH2PO4（99%）、Na2CO3（99.5%）、Mn(CH3COO)24H2O（99%）And MnF2
（99%）It is used as parent material.Each material is dissolved with the amount relative to solvent 0.06mol by distilling water as solvent.Will
The solution for being dissolved with each material adds to 250mL diethylene glycol（De-Ethyl-Glycol, DEG/C4H10O3）.Consider material
Reactivity is sequentially introduced into solution.Introduce a mixture into hydrothermal synthesis device, it is then small in 250rpm reactions 5 at 200 DEG C
When.During the course of the reaction, the internal pressure in hydrothermal synthesis device is maintained at about 8atm.After reaction, wash and do in absolute ethyl alcohol
The powder of dry gained is to remove impurity.Powder is centrifuged to remove DEG.The powder of gained is led into absolute ethyl alcohol, then
Stirring 30 minutes, and centrifuged to remove and organic substance produced after absolute ethyl alcohol reaction.The step is carried out 3 times
Or more time.Complete after washing step, in vacuum drying oven（60℃）Middle dried powder 12 hours or more.Under an argon atmosphere, make
It is heat-treated 6 hours in 400 DEG C of powder to gained with sintering furnace, to obtain LiMnPO4/Na2MnPO4F（1:1）Powder.
Comparative example 1
As steps described below LiMnPO is synthesized by Hydrothermal Synthesiss4.LiH is used with scheduled volume2PO4（99%）And Mn
(CH3COO)24H2O（99%）It is used as parent material.Dissolved in the distilled water as solvent with the amount relative to solvent 0.06mol
Each material.The solution for being dissolved with each material is led to 250mL diethylene glycol（De-Ethyl-Glycol, DEG/C4H10O3）.Examine
The reactivity for considering material is sequentially introduced into solution.Introduce a mixture into hydrothermal synthesis device, then at 180 DEG C in 250rpm
Reaction 5 hours.During the course of the reaction, the internal pressure of hydrothermal synthesis device is maintained at about 8atm.After reaction, obtained by washing and drying
Powder is to remove impurity.For washing step, absolute ethyl alcohol is used.Powder is centrifuged to remove DEG.By the powder of gained
Absolute ethyl alcohol is led to, is followed by stirring for 30 minutes.Gained powder is centrifuged produced by after being reacted with removing with absolute ethyl alcohol
Organic substance.The step is carried out 3 times or more times.Complete after washing step, in vacuum drying oven（60℃）Middle dried powder 12 hours
Or more.Under an argon atmosphere, it is heat-treated 6 hours in 400 DEG C of powder to gained using sintering furnace, to obtain LiMnPO4's
Powder.
Comparative example 2
As steps described below Na is synthesized by Hydrothermal Synthesiss2MnPO4F.NaH is used with scheduled volume2PO4（99%）、Na2CO3
（99.5%）、Mn(CH3COO)24H2O（99%）And MnF2（99%）It is used as parent material.With phase in the distilled water as solvent
Amount for solvent 0.06mol dissolves each material.The solution for being dissolved with each material is added to 250mL diethylene glycol（De-
Ethyl-Glycol, DEG/C4H10O3）.Consider that the reactivity of material is sequentially introduced into solution.Introduce a mixture into hydro-thermal conjunction
Into in device, then reacted 5 hours in 250rpm at 200 DEG C.During the course of the reaction, the internal pressure of hydrothermal synthesis device is maintained at about
8atm.After reaction, thus obtained powder is washed and dried to remove impurity.For washing step, anhydrous second is used
Alcohol.Powder is centrifuged to remove DEG.The powder of gained is led into absolute ethyl alcohol, is followed by stirring for 30 minutes.By gained powder
Centrifuged to remove and organic substance produced after absolute ethyl alcohol reaction.The step is carried out 3 times or more times.Complete washing
After step, in vacuum drying oven（60℃）Middle dried powder 12 hours or more.Under an argon atmosphere, it is right at 400 DEG C using sintering furnace
The powder of gained is heat-treated 6 hours, to obtain Na2MnPO4F powder.
Comparative example 3
LiMnPO is respectively synthesized according to comparative example 1 and 24And Na2MnPO4F.By the LiMnPO of synthesis4And Na2MnPO4F is with 1:
1 ratio mixing, and by ball milling and then uniform mixing, to obtain LiMnPO4/Na2MnPO4F（1:1）Blended powder.
Test example 1：Test to cathode material property
Pass through X-ray diffraction（XRD）The structure of the composite cathode material of embodiment 1 is detected, and diffraction is illustrated in Fig. 1
In.It was found that LiMnPO4It is accredited as with space group Pnma, and Na2MnPO4F is then accredited as with space group P21/n.By spreading out
Penetrate the strength ratio discovery at peak, LiMnPO4And Na2MnPO4F is with 1:1 ratio is present.
According to Li the and Na elementary analysis results detected through ICP, it was found that Li and Na are with 1:1 ratio is present.Thus demonstrate,prove
The real LiMnPO prepared by embodiment 14/Na2MnPO4The LiMnPO of F compounds4And Na2MnPO4The ratio between F is 1:1.
In order to determine LiMnPO4/Na2MnPO4LiMnPO in F compounds4And Na2MnPO4F form, carries out SEM and EDX
Map, and result is shown in Fig. 2 and Fig. 3.As shown in Fig. 2 SEM figures, there is two different kinds of particle in discovery, such as big
The particulate that small is a few micrometers of bulky grain and size is several nanometers.For further Accurate Analysis, EDX is carried out to each element and reflected
Penetrate, and result is shown in Figure 3.Found by EDX mapping results, size is Na for a few micrometers of bulky grain2MnPO4F, and size
It is LiMnPO for several nanometers of particulates4.The LiMnPO with variable grain shape and variable grain size is thereby determined that4With
Na2MnPO4F is intimately mix with one another.
Test example 2：Test to electrochemical properties
Using embodiment 1 and the powder of the cathode material compound of comparative example 3, by 95wt% cathode material compound with
5wt% adhesive PVdF mixing, then using 1-METHYLPYRROLIDONE（NMP）Slurry is prepared as solvent.
Slurry is coated on Al paper tinsels, thickness is 20 μm, then dries and is reinforced by pressing.Under vacuo in 120 DEG C
Products obtained therefrom is dried 16 hours, so as to obtain a diameter of 16mm circular electrode.
Punching press lithium metal foil using a diameter of 16mm uses polypropylene as to electrode（PP）Film is used as dividing plate.
In addition, being used in 1:1（v/v）The ethylene carbonate of ratio mixing（EC）And dimethoxy-ethane（DME）In LiPF containing 1M6's
Solution is used as electrolyte.By electrolyte-impregnated dividing plate, and dividing plate is located at working electrode and between electrode.Then, using shell
Body（SUS）Make electrode test battery, test the electrode performance of battery.
As shown in figure 4, it shows to include the charge/discharge of the battery of the cathode material prepared by embodiment 1 at room temperature
Curve map, it is found that there is the meadow of close limit at 3.8V, and battery is in the charge/discharge that scope is 2.0V to 4.8V
Under show 75mAhg-1Discharge capacity, and scope for 1.0V to 4.8V charge/discharge under show 161mAhg-1
Discharge capacity.Accordingly, it is determined that the LiMnPO4/Na2MnPO4F compounds can be used as electrode material.
Fig. 5 shows to include the charge/discharge curve map of the battery of the cathode material prepared by comparative example 3 at room temperature.Can
To determine, including there is no significance difference in terms of charge/discharge characteristics between the battery of embodiment 1 and the material including comparative example 3
Not.It is possible thereby to determine, compared to by mixing traditional blended mixts that two kinds of materials are obtained, it can be closed by an only step
Into come prepare according to the present invention LiMnPO4/Na2MnPO4The electrode material of F compounds, thus in manufacturing process and business efficiency
Aspect is favourable.
By reference to illustrative embodiments of the invention to the present invention have been described in detail.However, art technology
Personnel are it is understood that various change can be carried out to these embodiments in the case of without departing from the principle of the present invention and spirit
Become, the scope of the present invention is limited by appended claim and its equivalent way.
Claims (17)
1. a kind of cathode material, including lithium manganese phosphate LiMnPO4With manganese fluorophosphate sodium Na2MnPO4F compound, wherein by inciting somebody to action
The LiMnPO4With the Na2MnPO4F is with x LiMnPO4/1-x Na2MnPO4F(0<x<1) mixed proportion mixes to be formed
The cathode material, wherein the lithium manganese phosphate LiMnPO4With the manganese fluorophosphate sodium Na2MnPO4F has different crystal knots
Structure, and wherein described LiMnPO4Crystal structure there is space group Pnma, and the Na2MnPO4F crystal structure has sky
Between group P21/n。
2. cathode material as claimed in claim 1, also including all equally distributed carbonaceous conductive materials.
3. cathode material as claimed in claim 2, wherein the carbonaceous conductive material is selected from super-P, acetylene black and Ketjen black
It is any or its any combination.
4. cathode material as claimed in claim 2, wherein the cathode material is inorganic/organic composite material.
5. a kind of method of the cathode material described in manufacturing claims 1, including：
(i) by lithium (Li) oxide or its precursor, sodium (Na) oxide or its precursor, manganese (Mn) oxide or its precursor, phosphoric acid
Salt or the mixing of its precursor and fluoride or its precursor；
(ii) mixture of step (i) is synthesized by hydrothermal synthesis method, to produce powder；With
(iii) powder obtained by step (ii) is heat-treated.
6. method as claimed in claim 5, also including adding carbon material to the product of step (iii), and carries out ball milling to produce
The step of raw cathode material.
7. the heat treatment of method as claimed in claim 5, wherein step (iii) includes：
Fired 6 hours in 500 DEG C under argon (Ar) atmosphere.
8. method as claimed in claim 5, wherein the precursor of the oxidate for lithium is to be selected from lithium phosphate, lithium carbonate, hydroxide
Lithium, lithium acetate, lithium sulfate, lithium sulfite, lithium fluoride, lithium chloride, lithium bromide, lithium iodide and its any mixture it is any.
9. method as claimed in claim 5, wherein the precursor of the na oxide is to be selected from sodium phosphate, sodium carbonate, hydroxide
Sodium, sodium acetate, sodium sulphate, sodium sulfite, sodium fluoride, sodium chloride, sodium bromide and its any mixture it is any.
10. method as claimed in claim 5, wherein the precursor of the Mn oxide is to be selected from manganese Metal, manganese oxide, oxalic acid
Manganese, manganese acetate, manganese nitrate and its any mixture it is any.
11. method as claimed in claim 5, wherein the phosphatic precursor be selected from ammonium phosphate, sodium phosphate, lithium phosphate,
Potassium phosphate and its any mixture it is any.
12. method as claimed in claim 6, wherein the carbon material is appointing selected from super-P, acetylene black and Ketjen black
A kind of or its any combination.
It is small that 13. the synthetic reaction in method as claimed in claim 5, wherein step (ii) carries out 5 at 200 DEG C in 250rpm
When.
14. method as claimed in claim 13, wherein the synthetic reaction is carried out under 8atm pressure.
15. method as claimed in claim 5, wherein step (ii) also include：
The powder is washed by mixing 30 minutes with absolute ethyl alcohol；With
Powder/absolute ethyl alcohol mixture is centrifuged to remove organic material.
16. method as claimed in claim 15, wherein washing step are carried out 3 times or more times.
17. method as claimed in claim 15, is additionally included in 60 DEG C of vacuum drying powder/absolute ethyl alcohol mixtures 12 small
When or more.
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| IN2013CH05761A (en) | 2013-12-12 | 2015-08-07 | Pandian Bio Medical Res Ct | |
| CN105470473B (en) * | 2014-07-08 | 2018-12-04 | 宁德时代新能源科技股份有限公司 | Positive electrode active material and secondary battery |
| CN108493449B (en) * | 2018-03-20 | 2021-07-09 | 苏州大学 | A method for controllable preparation of sodium manganese fluorophosphate cathode material |
| KR102492040B1 (en) | 2021-01-08 | 2023-01-27 | 고려대학교 산학협력단 | Methods of producing cathode active material |
| CN114142003B (en) * | 2021-11-05 | 2024-02-23 | 成都佰思格科技有限公司 | Composite positive electrode slurry, lithium ion secondary battery and preparation method of lithium ion secondary battery |
| CN114883547B (en) * | 2022-05-20 | 2024-03-26 | 湖南钠邦新能源有限公司 | Na (Na) 2 Fe x M y PO 4 F@MF z @C composite material, preparation method thereof and application thereof in sodium ion battery |
| CN115132999A (en) * | 2022-07-15 | 2022-09-30 | 上海璞钠能源科技有限公司 | A kind of iron-based phosphate positive electrode for sodium battery and its preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284658A (en) * | 2008-05-20 | 2008-10-15 | 龚思源 | Compound phosphate type positive material of lithium ionic cell and method for making same |
| CN101714629A (en) * | 2009-11-10 | 2010-05-26 | 苏州大学 | Tri-platform blended cathode material for lithium ion batteries and preparation method thereof |
| CN101830451A (en) * | 2009-03-13 | 2010-09-15 | 中国科学院福建物质结构研究所 | Microwave hydro-thermal synthesis method of olivine type lithium ion battery positive pole material manganese lithium phosphate |
| JP2010260761A (en) * | 2009-05-01 | 2010-11-18 | Kyushu Univ | Method for producing positive electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery using the same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8057769B2 (en) | 2000-04-27 | 2011-11-15 | Valence Technology, Inc. | Method for making phosphate-based electrode active materials |
| US7041239B2 (en) | 2003-04-03 | 2006-05-09 | Valence Technology, Inc. | Electrodes comprising mixed active particles |
| JP4581525B2 (en) | 2004-07-23 | 2010-11-17 | 株式会社豊田中央研究所 | Positive electrode active material, method for producing the same, and lithium secondary battery |
| JP5431452B2 (en) * | 2008-04-07 | 2014-03-05 | カーネギー メロン ユニバーシティ | Aqueous electrolyte-based electrochemical secondary energy storage device using sodium ions |
| WO2009131095A1 (en) * | 2008-04-25 | 2009-10-29 | 住友大阪セメント株式会社 | Method for production of cathode active material for lithium ion battery, cathode active material for lithium ion battery produced by the method, electrode for lithium ion battery, and lithium ion battery |
| US9786944B2 (en) * | 2008-06-12 | 2017-10-10 | Massachusetts Institute Of Technology | High energy density redox flow device |
| KR20100133231A (en) * | 2009-06-11 | 2010-12-21 | 주식회사 엘앤에프신소재 | Cathode active material for lithium secondary battery, method for manufacturing same and lithium secondary battery comprising same |
| US9065117B2 (en) * | 2010-01-14 | 2015-06-23 | Johns Manville | Glass-fiber containing composite materials for alkali metal-based batteries and methods of making |
-
2011
- 2011-11-30 KR KR1020110127265A patent/KR101352793B1/en active Active
-
2012
- 2012-05-31 US US13/484,715 patent/US8906254B2/en active Active
- 2012-06-05 DE DE102012209462A patent/DE102012209462A1/en active Pending
- 2012-06-15 CN CN201210202773.9A patent/CN103137969B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284658A (en) * | 2008-05-20 | 2008-10-15 | 龚思源 | Compound phosphate type positive material of lithium ionic cell and method for making same |
| CN101830451A (en) * | 2009-03-13 | 2010-09-15 | 中国科学院福建物质结构研究所 | Microwave hydro-thermal synthesis method of olivine type lithium ion battery positive pole material manganese lithium phosphate |
| JP2010260761A (en) * | 2009-05-01 | 2010-11-18 | Kyushu Univ | Method for producing positive electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery using the same |
| CN101714629A (en) * | 2009-11-10 | 2010-05-26 | 苏州大学 | Tri-platform blended cathode material for lithium ion batteries and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Comparative Kinetic Study of Olivine LixMPO4 (M = Fe, Mn);Masao Yonemura, Atsuo Yamada, Yuki Takei et al;《Journal of The Electrochemical Society》;20040809;第151卷(第9期);全文 * |
| Ionothermal Synthesis of Sodium-Based Fluorophosphate Cathode Materials;N. Recham, J-N. Chotard, L. Dupont et al;《Journal of The Electrochemical Society》;20091007;第156卷(第12期);第A994页第2段 * |
| Sol-gel synthesis and electrochemical properties of fluorophosphates Na2Fe1-xMnxPO4F/C (x = 0, 0.1, 0.3, 0.7, 1) composite as cathode materials for lithium ion battery;Xiaobiao Wu, Jianming Zheng, Zhengliang Gong et al;《Journal of Materials Chemistry》;20111024;第21卷(第46期);全文 * |
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